Use of diol alkoxylates as additives for the production of pigment concentrates

ABSTRACT

Pigment concentrates comprising a pigment, a liquid carrier medium and a diol alkoxylate of the general formulae (I), (II) and/or (III) are described in conjunction with methods of preparing the same. The diol alkoxylates described and used herein are of the general formulae (I), (II) and/or (III):                    
     wherein each of R 1 , R 2 , R 3 , R 5 , R 7  and R 8  independently represents a hydrogen atom or an alkyl group having from 1 to about 36 carbon atoms, with the proviso that both R 1  and R 2  are not simultaneously hydrogen atoms and the total number of carbon atoms in R 1  and R 2  is from about 6 to about 38, and with the proviso that both R 3  and R 5  are not simultaneously hydrogen atoms and the total number of carbon atoms in R 3  and R 5  is from about 6 to about 38, wherein R 4  represents a linear or branched alkylene group having from about 2 to about 12 carbon atoms or (—CH 2 —CHR 6 —O) z —, wherein R 6  represents a hydrogen atom or a methyl group, wherein each of x and y independently represent a number of from about 1 to about 200, z represents a number of from about 1 to about 20, n represents a number of from about 2 to about 12, and wherein the sum of x+y is a number of from about 5 to about 200.

BACKGROUND OF THE INVENTION

Pigment concentrates are prepared by breaking down pigments with the aidof shear machines in a liquid carrier medium and dispersing them sofinely that the pigment is permanently in the form of the primaryparticles. Suitable shear machines are known to the skilled worker andare described with particular attention to American technologies in, forexample

C.H. Hare, Protective Coatings—Fundamentals of Chemistry andComposition, Technology Publishing Comp., Pittsburg (1994).

Owing to the importance of dispersing for the varnish, paint andprinting ink industry, both the dispersing process and the low andhigher molecular mass compounds suitable for stabilizing the primaryparticles are described at length in the technical literature. By way ofexample, reference may be made here to:

H. Kittel, Lehrbuch der Lacke und Beschichtungen, Vol. III, p. 239 ff.,Verl. W. A. Colomb, Berlin, Oberschwandorf (1976)

J.V. Robinson, R. N. Thompson, Dispersants, in Paper Coating Additives,Monograph No. 25, TAPPI, Atlanta 1963

J. D. Schofield, Polymeric Dispersants, in Handbook of Co a tingAdditives, L. J. Calbo (Ed.) Vol. 2, Marcel Dekker, New York, Basel,Hong Kong (1992).

From the known prior art it is not possible to derive any teachingrelating to the targeted selection of additives which effectivelysupport the formulation of pigment concentrates, especially when thesepigment concentrates are intended to allow the preparation oflow-emissions or emissions-free paints and printing inks or when theyare to be free from environmentally or ecotoxicologically unacceptablesubstances.

A particular difficulty is represented by the formulation of aqueouspigment concentrates, especially when these concentrates are to beformulated without the addition of low molecular mass cosolvents such asethylene glycol or propylene glycol. Thus, as the skilled worker isaware, so-called pigment dispersants based on polyphosphates orpolyacrylates, although outstandingly suitable for maintaining pigmentsand fillers in suspension alongside the emulsifier-stabilized orprotective-colloid-stabilized latex particles in emulsion paints, areunsuitable for preparing pigment concentrates having the profile ofrequirements described above.

The majority of dispersants, which are of outstanding suitability inorganic carrier oils of different polarities, fail if water is chosen asthe continuous phase for the pigment concentrates. Surfactant-typedispersants which provide good pigment wetting, such as alkylphenolpolyglycol ethers—see, for instance, patent GB 861 223—in turn have comeunder environmental debate in recent times in respect of theirbiodegradability, both in the laundry detergent and cleaning productsindustries, where they have already been fully replaced as surfactantsin Germany, and in emulsion polymerization, i.e., in the production ofaqueous binders for emulsion paints; in this context see:

C. Baumann, D. Feustel, U. Held, R. Höfer, “Stabilisierungssysteme fürdie Herstellung von Polymer-Dispersionen” [Stabilizing Systems forPreparing Polymer Dispersions] in: Welt der Farben, p. 15ff., (2/1996).

A further difficulty in respect of selecting additives to formulatepigment concentrates is that the dispersing additive must be selectedsuch that, substantially independently of the carrier oil, the viscosityof the continuous phase decreases as the shear force increases; i.e.,the dispersion must possess pseudoplasticity and must in no case bedilatant.

When formulating pigment concentrates care must further be taken toestablish a special balance between water retention capacity andhygroscopy such that the intrinsic drying of the concentrate is greatlyretarded. Partially dried pigment concentrates should be readilyredispersible. On the other hand, water retention capacity andhygroscopy must not be so high that the finished coating becomessensitive to water.

Other service properties of the finished paint as well, such asfreeze/thaw stability, storage stability, and shear stability, must notbe adversely affected, with the same applying to properties of the curedfilm, e.g., clarity, gloss, or resistance to blushing.

A further particular requirement to be met by the pigment concentratesto be developed in accordance with the invention is that there must becompatibility with a broad spectrum of binders, organic and inorganicpigments, which in turn are usually present dispersed in what are knownas base coats, and at the same time both with water and with thedifferent solvents used in paints, and also with the highly alkalinewaterglasses used in silicate paints.

A high percentage of liquid paints are produced industrially bypreparing the polymeric binder in a separate stage and then blending itwith the other ingredients to form the finished paint. If coloration isto take place at this point rather than later, the pigment is dispersedwith the binder in an upstream stage in a high-speed mixer or in adissolver, and is then diluted down to use concentration. Of particularinterest in connection with this invention are architectural paints forhome improvement use and for the craft sector, both for interior andexterior coatings. The binders for these paints are prepared by emulsionpolymerization in aqueous phase. In practice, the aqueous phasefrequently comprises volatile organic solvents, known as coalescents,which are added either during the polymerization or later and whichassist in film formation by partially dissolving the latex particles andalso promote leveling. The inherent odor of these coalescents,especially that of the known and widespread2,2,4-trimethyl-3-hydroxypentyl isobutyrate (Texanol®), can be perceivedfor several days in freshly painted rooms. In modern-day society,however, this odor is increasingly found to be a nuisance. There istherefore interest in keeping modern paints totally free from suchcoalescents and other volatile solvents or cosolvents and in also notintroducing such ingredients via the pigment concentrates either.

Besides the coloring of paints during production, a significantpercentage are not colored until immediately before their use, whetherin order to establish special shades or for the purpose of meetingparticular customer wishes. In these cases, an industriallypremanufactured pigment concentrate is admixed to a white or pastelstock paint. This near customer form of color adjustment can be doneeither by tradespersons or on a semi-industrial or industrial basis. Inthese cases the pigment concentrate is usually admixed in a proportionof from 5 to 200 ml per l of stock paint. Often, a combination of two orthree different pigment pastes is required in order to arrive at thedesired shade. The pigment concentrates commonly comprise high pigmentconcentrations; i.e., the pigment volume concentration—abbreviated topvc—is normally between 10 and 80%.

DE-A-26 28 145 discloses adducts of ethylene oxide on specific glycols,containing a —C≡C— group as structural element. These compounds are saidto be suitable as moisteners, dispersants, nonionic antifoams, andviscosity stabilizers, and to develop their action in aqueous solutionat a lower concentration than in the case of conventional surfactants.Other than listing the abovementioned areas of application, however,DE-A-26 28 145 does not disclose any specific further details orexemplary embodiments.

EP 565 709 Bl discloses aqueous inkjet inks which includepolyol-alkylene oxide condensates as a cosolvent. According to page 4,lines 9-15 of this document, the polyol contains in particular three ormore OH groups. There is explicit mention of specific triols such asglycerol, trimethylolpropane, trimethylolethane, 1,2,4-butanetriol, and1,2,6-hexanetriol, and also of pentaerythritol anddi(trimethylolpropane) as tetrols, glucose as a pentol, and sorbitol andinositol as hexols. The use of diols, however, is said to be fairlyunsatisfactory. It is found in this context that alkylene oxidecondensates of diols are generally not compatible with pigmentdispersions, with the possible exception of neopentyl glycolalkoxylates.

WO 96/7689 discloses copolymers of the general formula (A—COO)₂—B, inwhich A has a molar weight of at least 500 and is the residue of anoil-soluble complex monocarboxylic acid of specific structure and B hasa molar weight of at least 500 and is the divalent radical of an alkylglycol or of a polyalkylene glycol. The copolymers of WO 96/7689 aresaid to be suitable for dispersing inorganic pigments in organic media.

EP 735 109 A2 discloses aqueous pigment preparations containing interalia from 10 to 80% of a pigment and from 0.1 to 20% of an alkoxylationproduct obtained by adding optionally substituted styrenes ontooptionally substituted phenols and reacting the adducts with ethyleneoxide and/or propylene oxide.

DE 39 20 130 A1 discloses the use of partial esters of oligoglycerolswith fatty acids as pigment dispersants for aqueous paint dispersions.Said partial esters can if desired have been ethoxylated and/orpropoxylated.

The present invention was based on the object of providing effectiveadditives for preparing pigment concentrates, and the pigmentconcentrates thereby obtainable themselves, which meet the large numberof abovementioned criteria relating to the desirable profile ofproperties of such additives and, respectively, of the pigmentconcentrates themselves.

BRIEF SUMMARY OF THE INVENTION

The present invention includes the use of diol alkoxylates of thegeneral formulae (I), (II) and (III) in the preparation of pigmentconcentrates, and includes methods or preparing the same. The presentinvention also includes pigment concentrates comprising a pigment, adiol alkoxylate of the general formulae (I), (II) and/or (III), and aliquid carrier medium. Pigment concentrates of the present invention arepreferably aqueous, and thus, the preferred liquid carrier medium iswater.

The invention provides first of all for the use of diol alkoxylates asadditives for preparing pigment concentrates. Said diol alkoxylates areselected from the group of compounds of the formulae (I) to (III).

The compounds (I) to (III) have the following structures:

in which

the radicals R¹ and R² independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the radicals R³ and R⁵ independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the radical R⁴ is a straight-chain or branched alkylene group having 2to 12 carbon atoms or a group (—CH₂—CHR⁶—O)_(z),

the radical R⁶ is hydrogen or a methyl group,

the radicals R⁷ and R⁸ independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the indices x and y independently of one another are numbers in therange from 1 to 200,

the index z is a number in the range from 1 to 20, and

the index n is a number in the range from 2 to 12,

with the further proviso that

radicals R¹ and R² must not both simultaneously be hydrogen,

the sum of the carbon atoms in the radicals R¹ and R² is in the rangefrom 6 to 38,

radicals R³ and R⁵ must not both simultaneously be hydrogen,

the sum of the carbon atoms in the radicals R³ and R⁵ is in the rangefrom 6 to 38,

the sum (x+y) is a number in the range from 5 to 200.

For preferred embodiments, in the compounds of the formulae (I) to(III), independently of one another

the radicals R¹ and R² and, respectively, R³ and R5 are alkyl groupshaving 12 to 18 carbon atoms, and

the sum (x+y) is a number in the range from 5 to 120.

In one preferred embodiment the present invention provides for the useof the diol alkoxylates (I) to (III) as additives for preparing aqueouspigment concentrates.

The amount of diol alkoxylates to be used in accordance with theinvention depends firstly on the nature of the colorants to be dispersedand also on the amount of the colorants to be dispersed. The compounds(I), (II) and (III) are preferably used in an amount of from 0.1 to 20%by weight, based on the overall pigment dispersion.

DETAILED DESCRIPTION OF THE INVENTION

The compounds (I) to (III) can be prepared by any methods known to theskilled worker from the literature. As a general rule, a diol isprepared first of all and is then alkoxylated by customary methods. Thestandard method of alkoxylation is to contact an alcohol—in the case ofthe present invention a diol—with ethylene oxide and/or propylene oxideand to react this mixture in the presence of an alkaline catalyst attemperatures in the range from 20 to 200° C. In this way, adducts ofethylene oxide (EO) and/or propylene oxide (PO) with the respective diolused are obtained. The adducts therefore include EO adducts or POadducts or EO/PO adducts with the particular diol used; in the case ofthe EO/PO adducts, the addition of EO and PO can take place randomly orclockwise.

Representative Examples of the Preparation of Compounds (I)

Reaction of relatively long-chain epoxides, obtainable by knownprocesses from olefins of a wide variety of origins by epoxidation, withethylene glycol in a molar ratio of 1:1 in the presence of alkaline oracidic catalysts, and subsequent ethoxylation of the resultant products.

For example, an α-olefin epoxide having 14 carbon atoms is reacted withethylene glycol in a molar ratio of 1:1. Subsequently, the desiredamount of ethylene oxide and/or propylene oxide is added onto theresultant diol.

Representative Examples of the Preparation of Compounds (II)

Reaction of relatively long-chain epoxides, obtainable by knownprocesses from olefins of a wide variety of origins by epoxidation, withethylene glycol in a molar ratio of 2:1 in the presence of alkaline oracidic catalysts, and subsequent ethoxylation of the resultant products.

For example, an α-olefin epoxide having 16 carbon atoms is reacted withethylene glycol in a molar ratio of 2:1. Subsequently, the desiredamount of ethylene oxide and/or propylene oxide—for example, 10 mol ofethylene oxide per mole of the diol—is added onto the resultant diol.

Representative Examples of the Preparation of Compounds (III)

12-Hydroxystearyl alcohol is obtainable by hydrogenating methylricinoleate. This diol can be ethoxylated to give compounds of type(III). Further compounds of type (III) are obtained by alkoxylatingα,ω-alkanediols, such as 1,10-decanediol or 1,12-dodecanediol.

The compounds (I) to (III) present in the pigment concentrates of theinvention are nitrogen-free and free from hydrolyzable ester or aldehydegroups.

The present invention further provides pigment concentrates comprising

a) from 10 to 80% by weight of one or more pigments,

b) from 0.1 to 20% by weight of one or more diol alkoxylates from thegroup of compounds of the formulae (I) to (III)

 in which

the radicals R¹ and R² independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the radicals R³ and R^(s) independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the radical R⁴ is a straight-chain or branched alkylene group having 2to 12 carbon atoms or a group (—CH₂—CHR⁶—O)_(z—,)

the radical R⁶ is hydrogen or a methyl group,

the radicals R⁷ and R⁸ independently of one another are alkyl groupshaving 1 to 36 carbon atoms or hydrogen,

the indices x and y independently of one another are numbers in therange from 1 to 200,

the index z is a number in the range from 1 to 20, and

the index n is a number in the range from 2 to 12,

with the further proviso that

radicals R¹ and R² must not both simultaneously be hydrogen,

the sum of the carbon atoms in the radicals R¹ and R² is in the rangefrom 6 to 38,

radicals R³ and R⁵ must not both simultaneously be hydrogen,

the sum of the carbon atoms in the radicals R³ and R⁵ is in the rangefrom 6 to 38,

the sum (x+y) is a number in the range from 5 to 200, and

c) from 15 to 85% by weight of a liquid carrier medium.

As far as the selection of the pigments a) is concerned, there are norestrictions per se whatsoever in the context of the present invention.As is known to the skilled worker, pigments comprise particulate organicor inorganic substances which are virtually insoluble in solvents orbinders and which may either be color-imparting themselves or flatting.Many inorganic pigments also function as fillers, and vice versa.Examples of particularly widespread classes of pigments can be found inthe relevant technical literature, for instance:

Otto-Albrecht Neumüller, Römpps Chemie-Lexikon, 7^(th) edition,Stuttgart 1974, pages 2693-2695

Liquid carrier media c)—for instance, organic carrier oils or water—areknown to the skilled worker. In one preferred embodiment the liquidcarrier medium chosen is water. In this case, therefore, the pigmentconcentrates are aqueous.

In another embodiment, the pigment concentrates of the invention containnot only the obligatory ingredients a), b) and c) but also from 0.1 to30% by weight of one or more surfactants d) from the group of alkylpolyglycosides (as described in more detail below), fatty alcoholpolyglycol ethers (as described in more detail below), and styrylphenolpolyglycol ethers (as known, for instance, from the abovementionedEP-A-735 109).

Alkyl polyglycosides can be characterized by the general structure (IV):

R—(G)_(p)  (IV)

In this formula, R denotes a linear, saturated alkyl radical having 8 to22 carbon atoms and (G)_(p) denotes a glycoside or oligoglycosideradical having a degree of oligomerization, p, of from 1 to 10. Alkylglycosides of the stated formula (IV) are long-establishedsurface-active substances which can be prepared from sugars and fromaliphatic, primary alcohols having 8 to 22 carbon atoms byacetalization. Suitable sugar components (glycoses) are preferablyglucose, but also fructose, mannose, galactose, telose, gulose, allose,altrose, idose, arabinose, xylose, lyxose, libose and mixtures thereof.Preferred on account of their ready availability and good performanceproperties are the acetalization products of glucose with fattyalcohols, which are obtainable, for example, from natural fats and oilsby known processes, especially those with linear, primary, saturated andunsaturated fatty alcohols having 8 to 22 carbon atoms. In respect ofthe glycoside radical (G)_(p), both monoglycosides (p=1), in which onesugar residue is linked glycosidically to the fatty alcohol, andoligomeric glycosides, having a degree of oligomerization p=2 to 10, aresuitable. In general, mixtures of mono- and oligoglycosides are present.Preferred and suitable alkyl glycosides (IV) are those in which R is analkyl group having 8 to 22 carbon atoms and (G)_(p) is a glycoside oroligoglycoside radical having a degree of oligomerization p=1 to 10.With very particular preference, R is an alkyl group having 8 to 14carbon atoms. The average degree of oligomerization is preferably in therange from 1 to 1.5.

Fatty alcohol polyglycol ethers can be characterized by the generalformula (V):

R⁹—O—(CH₂—CHR¹⁰—O)_(q)H  (V)

In this formula, R⁹ is a linear, saturated alkyl radical having 8 to 22carbon atoms, the radical R¹⁰ is hydrogen or a methyl group, and theindex q is a number in the range from 1 to 50. Among the group of thecompounds (V), particular preference is given to fatty alcoholethoxylates, especially adducts of from 2 to 20 mol of ethylene oxideper mole of fatty alcohol having 12 to 18 carbon atoms.

In another embodiment the pigment concentrates of the invention containnot only the obligatory ingredients a), b) and c) but also from 0.1 to30% by weight of one or more coadditives e) from the group ofpolyethylene glycols and polyglycol ethers (obtainable by ethoxylating1,2- or 1,3-propanediol, 1,2-1,4-butanediol, hexanediol, glycerol,trimethylolpropane or pentaerythritol), which compounds should have amolecular weight in the range from 200 to 1000, preferably from 200 to600.

In addition to said obligatory ingredients a), b) and c) the pigmentconcentrates of the invention may additionally comprise furtherconstituents which are customary in pigment concentrates. Examples ofsuch constituents are defoamers, preservatives, drying retardants, andantisettling agents.

The pigment concentrates of the invention are suited to the coloring ofpaints by, for example, the home improver or by the skilled worker inpaint banks, or else at the premises of the paints manufacturer.However, the pigment concentrates of the invention may likewise be usedfor coloring other coatings, such as printing inks, leather dressings,wallpaper colors, wood varnishes, wood preservative systems andwoodstains, overprint varnishes, or air-drying or oven-drying industrialcoatings, and for pigmenting colored pencil leads, fiber tip pens,inkjet inks, graphics inks, pastes for ballpoint pens, shoe polishes,nonwoven webs, colored paper coating slips and paper pulp colorings,printing inks for cardboard, spin-dyeing colorants, and films.

The examples which follow serve to illustrate the invention and shouldnot be understood as limitative.

EXAMPLES 1. Substances Used

1.1. Pigments

PR 101: Pigment with Colour Index PR (Pigment Red) 101; “Bayferrox 120M” (from Bayer) was used for this

PV 19: Pigment with Colour Index PV (Pigment Violet) 19; “Hostapermrotviolett ER 02” (from Hoechst AG) was used for this

PG 7: Pigment with Colour Index PG (Pigment Green) 7; “Sunfast grün 7264-0414” (from Sun Chemicals) was used for this

PBk 7: Pigment with Colour Index PR (Pigment Black) 7; “Spezialschwarz4” (from Degussa) was used for this

1.2. Antisettling Agent

Xanthan gum “Deuteron VT 819” (Wilhelm O. C. Schöner GmbH, Achim)

1.3. Defoamer

Silicone defoamer “Dehydran 3282” (Henkel KGaA, Düsseldorf)

1.4. Additives of the Invention

Add-1: Compound of the general formula (I) where R¹ is a linearC_(10/12) alkyl radical, the radicals R² and R⁶ are hydrogen, and thesum (x+y) is 10.

1.5. White Emulsion Paints and Dispersion Lacquers

Disp-1: Emulsion paint based on vinyl acetate-ethylene copolymer(“Vinnapast EZ 36”, Wacker Chemie)

Disp-2: Emulsion paint based on styrene acrylate (“Acronal 290D”, BASF)

Disp-3: Dispersion lacquer based on all-acrylate (“Neocryl XK90”, ZenecaResins/NL)

2. Preparation of the Pigment Pastes (pigment concentrates) 2.1. ExampleB-1

34.9 parts by weight of water were introduced as an initial charge, 4.5parts by weight of the additive Add-1 were added with stirring, and thismixture was homogenized. Then 60 parts by weight of the pigment PR 101were added and the mixture was homogenized using a dissolver (DispermatCV, from Getzmann, Reinhardshagen). Dimethylethanolamine was addedcarefully to the premix obtained in this way, in an amount such as togive a pH of 8. Subsequently, 0.4 part by weight of the defoamerspecified under 1.3. and 0.2 part by weight of the antisettling agentspecified under 1.2. were added and the mixture was dispersed using astirred ball mill in a circulation process (Dispermat SL, from Getzmann,Reinhardshagen) for 30 minutes at a speed of 2000 revolutions perminute.

2.2. Example B-2

57.6 parts by weight of water were introduced as an initial charge, 12parts by weight of the additive Add-1 were added with stirring, and thismixture was homogenized. Then 30 parts by weight of the pigment PV 19were added and the mixture was homogenized using a dissolver (DispermatCV, from Getzmann, Reinhardshagen). Dimethylethanolamine was addedcarefully to the premix obtained in this way, in an amount such as togive a pH of 8. Subsequently, 0.4 part by weight of the defoamerspecified under 1.3. was added and the mixture was dispersed using astirred ball mill in a circulation process (Dispermat SL, from Getzmann,Reinhardshagen) for 60 minutes at a speed of 3500 revolutions perminute.

2.3. Example B-3

48.6 parts by weight of water were introduced as an initial charge, 11parts by weight of the additive Add-1 were added with stirring, and thismixture was homogenized. Then 40 parts by weight of the pigment PG 7were added and the mixture was homogenized using a dissolver (DispermatCV, from Getzmann, Reinhardshagen). Dimethylethanolamine was addedcarefully to the premix obtained in this way, in an amount such as togive a pH of 8. Subsequently, 0.4 part by weight of the defoamerspecified under 1.3. was added and the mixture was dispersed using astirred ball mill in a circulation process (Dispermat SL, from Getzmann,Reinhardshagen) for 60 minutes at a speed of 4000 revolutions perminute.

2.4. Example B-4

59.6 parts by weight of water were introduced as an initial charge, 15parts by weight of the additive Add-1 were added with stirring, and thismixture was homogenized. Then 25 parts by weight of the pigment PBk 7were added and the mixture was homogenized using a dissolver (DispermatCV, from Getzmann, Reinhardshagen). Dimethylethanolamine was addedcarefully to the premix obtained in this way, in an amount such as togive a pH of 8. Subsequently, 0.4 part by weight of the defoamerspecified under 1.3. was added and the mixture was dispersed using astirred ball mill in a circulation process (Dispermat SL, from Getzmann,Reinhardshagen) for 90 minutes at a speed of 4000 revolutions perminute.

3. Performance Investigations

The pigment pastes obtained according to 2.1. to 2.4. (Examples B-1 toB-4) were tested for their viscosity behavior and for theircompatibility with white emulsion paints and dispersion lacquers. Theresults can be found from Tables 1 to 3.

3.1. Viscosity Behavior

The viscosities of the pigment pastes of Examples B-1 to B-4 weremeasured

a) after storage at 20° C. for 24 hours, and

b) after storage at 40° C. for 4 weeks,

at room temperature by the Brookfield method (LVT, 30 revolutions perminute, spindle 2-4, after stirring time of 1 minute); the figures inTable 1 are in mPas.

TABLE 1 Viscosity behavior B-1 B-2 B-3 B-4 Viscosity after 24 hrs 5003500 300 150 Viscosity after 4 weeks 540 3200 320 160

3.2. Rubout

To determine the rubout, the white emulsion paints and lacquers Disp-1to Disp-3 were each admixed with 10% by weight—based on the whiteemulsion paint or dispersion lacquer employed—of the pigment pastesaccording to Examples B-1 to B-4 and the mixtures were homogenized. Theresulting formulations were then applied

a) immediately, and

b) after storage at 40° C. for 4 weeeks

in a thin film (150 micrometers' wet-film thickness) to paper contrastcharts (from Erichsen, Type “7.32/7”). After about 3 minutes, theapplied mixture was rubbed with the finger in the lower third of thetest chart and then the colors of the unrubbed area were compared withthe color of the rubbed area (using Dr. Lange MicroColor in accordancewith CIELAB, illuminant D65, 10°). The resulting ΔE values are reportedin Tables 2a (formulations used directly) and 2b (formulations storedfor 4 weeks). As the skilled worker is aware, in the technical sector atissue here, ΔE values in the region of from 0.3 to 0.5 are classified asvery good, ΔE values in the region of from 0.5 to about 1.0 areclassified as good, and ΔE values of more than 1.0 are classified asunacceptable.

TABLE 2a Rubout on direct use of the formulations B-1 B-2 B-3 B-4 Disp-10.6 0.4 0.5 0.5 Disp-2 0.5 0.3 0.5 0.4 Disp-3 0.6 0.4 0.3 0.3

TABLE 2b Rubout on 4-week storage of the formuiations B-1 B-2 B-3 B-4Disp-1 0.6 0.5 0.6 0.6 Disp-2 0.5 0.3 0.5 0.4 Disp-3 0.5 0.4 0.3 0.4

3.3. Degree of Gloss

To determine the degree of gloss, the white emulsion paints and lacquersDisp-1 to Disp-3 were each admixed with 10% by weight—based on the whiteemulsion paint or dispersion lacquer employed—of the pigment pastesaccording to Examples B-1 to B-4 and the mixtures were homogenized. Theresulting formulations were then applied

a) immediately, and

b) after storage at 40° C. for 4 weeks

in a thin film (150 micrometers' wet-film thickness) to paper contrastcharts (from Erichsen, Type “7.32/7”). After drying, the degree of glosswas determined at angles of 85° or 60° using a Dr. Lange degree of glossmeasuring instrument. The results are reported in Tables 3a(formulations used directly) and 3b (formulations stored for 4 weeks)For comparison, the degree of gloss of the white emulsion paints anddispersion lacquers was also determined, i.e., of the unmodified polymerdispersions Disp-1 to Disp-3 not tinted with the pigment pastes B-1 toB-4 of the invention. These reference values are entered for purposes ofcomparison in Tables 3a and 3b in the column headed “reference”.

TABLE 3a Degree of gloss on direct use of the formulations Measurementangle Reference B-1 B-2 B-3 B-4 Disp-1 85° 3 3 3 3 3 Disp-2 85° 5 5 5 55 Disp-3 60° 44 43 45 46 44

TABLE 3b Degree of gloss on 4-week storage of the formulationsMeasurement angle Reference B-1 B-2 B-3 B-4 Disp-1 85° 3 3 3 3 3 Disp-285° 5 5 5 5 5 Disp-3 60° 45 44 44 45 45

What is claimed is:
 1. A method of preparing a pigment concentrate, saidmethod comprising: (a) providing at least one diol alkoxylate selectedfrom the general formulae (I), (II) and (III);

(b) combining the at least one diol alkoxylate with a pigment and aliquid carrier medium; and (c) mixing the at least one diol alkoxylate,the pigment and the liquid carrier medium to form a pigment concentrate;wherein each of R¹, R², R³, R⁵, R⁷ and R⁸ independently represents ahydrogen atom or an alkyl group having from 1 to about 36 carbon atoms,with the proviso that both R¹and R² are not simultaneously hydrogenatoms and the total number of carbon atoms in R¹ and R² is from about 6to about 38, and with the proviso that both R³ and R⁵ are notsimultaneously hydrogen atoms and the total number of carbon atoms in R³and R⁵ is from about 6 to about 38, wherein R⁴ represents a linear orbranched alkylene group having from about 2 to about 12 carbon atoms or(—CH₂—CHR⁶—O)_(z), wherein R⁶ represents a hydrogen atom or a methylgroup, wherein each of x and y independently represent a number of fromabout 1 to about 200, z represents a number of from about 1 to about 20,n represents a number of from about 2 to about 12, and wherein the sumof x+y is a number of from about 5 to about
 200. 2. The method accordingto claim 1, wherein each of R¹, R², R³ and R⁵ independently representsan alkyl group having from about 12 to about 18 carbon atoms, andwherein the sum of x+y is a number of from about 5 to about
 120. 3. Themethod according to claim 1, wherein the at least one diol alkoxylate isrepresented by the general formula (1), wherein R¹ represents a linearalkyl radical having from about 10 to about 12 carbon atoms, each of R²and R⁶ is a hydrogen atom, and wherein the sum of x+y is about
 10. 4.The method according to claim 1, wherein the at least one diolalkoxylate is present in an amount of from about 0.1 to about 20% byweight, based on the total weight of the pigment concentrate.
 5. Themethod according to claim 2, wherein the at least one diol alkoxylate ispresent in an amount of from about 0.1 to about 20% by weight, based onthe total weight of the pigment concentrate.
 6. The method according toclaim 3, wherein the at least one diol alkoxylate is present in anamount of from about 0.1 to about 20% by weight, based on the totalweight of the pigment concentrate.
 7. The method according to claim 1,wherein the liquid carrier medium comprises water.
 8. The methodaccording to claim 4, wherein the liquid carrier medium comprises water.9. A pigment concentrate comprising a pigment, a liquid carrier mediumand at least one diol alkoxylate of the general formulae (I), (II) and(III):

wherein each of R¹, R², R³, R⁵, R⁷ and R⁸ independently represents ahydrogen atom or an alkyl group having from 1 to about 36 carbon atoms,with the proviso that both R¹ and R² are not simultaneously hydrogenatoms and the total number of carbon atoms in R¹ and R² is from about 6to about 38, and with the proviso that both R³ and R⁵ are notsimultaneously hydrogen atoms and the total number of carbon atoms in R³and R⁵ is from about 6 to about 38, wherein R⁴ represents a linear orbranched alkylene group having from about 2 to about 12 carbon atoms or(—CH₂—CHR⁶—O)_(z), wherein R⁶ represents a hydrogen atom or a methylgroup, wherein each of x and y independently represent a number of fromabout 1 to about 200, z represents a number of from about 1 to about 20,n represents a number of from about 2 to about 12, and wherein the sumof x+y is a number of from about 5 to about
 200. 10. The pigmentconcentrate according to claim 9, wherein each of R¹, R², R³ and R⁵independently represents an alkyl group having from about 12 to about 18carbon atoms, and wherein the sum of x+y is a number of from about 5 toabout
 120. 11. The pigment concentrate according to claim 9, wherein theat least one diol alkoxylate is represented by the general formula (I),wherein R¹ represents a linear alkyl radical having from about 10 toabout 12 carbon atoms, each of R² and R⁶ is a hydrogen atom, and whereinthe sum of x+y is about
 10. 12. The pigment concentrate according toclaim 9, wherein the pigment is present in an amount of from about 10 toabout 80% by weight, the liquid carrier medium is present in an amountof from about 15 to about 85% by weight, and the at least one diolalkoxylate is present in an amount of from about 0.1 to about 20% byweight, all percent weights being based on the total weight of thepigment concentrate.
 13. The pigment concentrate according to claim 10,wherein the pigment is present in an amount of from about 10 to about80% by weight, the liquid carrier medium is present in an amount of fromabout 15 to about 85% by weight, and the at least one diol alkoxylate ispresent in an amount of from about 0.1 to about 20% by weight, allpercent weights being based on the total weight of the pigmentconcentrate.
 14. The pigment concentrate according to claim 9, whereinthe pigment is present in an amount of from about 25 to about 60% byweight, the liquid carrier medium is present in an amount of from about30 to about 60% by weight, and the at least one diol alkoxylate ispresent in an amount of from about 4 to about 15% by weight, all percentweights being based on the total weight of the pigment concentrate. 15.The pigment concentrate according to claim 10, wherein the pigment ispresent in an amount of from about 25 to about 60% by weight, the liquidcarrier medium is present in an amount of from about 30 to about 60% byweight, and the at least one diol alkoxylate is present in an amount offrom about 4 to about 15% by weight, all percent weights being based onthe total weight of the pigment concentrate.
 16. The pigment concentrateaccording to claim 9, wherein the liquid carrier medium comprises water.17. The pigment concentrate according to claim 9, further comprising atleast one surfactant selected from the group consisting ofalkylpolyglycosides, fatty alcohol polyglycol ethers, and styrylphenolpolyglycol ethers.
 18. The pigment concentrate according to claim 17,wherein the at least one surfactant is present in an amount of fromabout 0.1 to about 30% by weight, based on the total weight of thepigment concentrate.
 19. The pigment concentrate according to claim 9,further comprising at least one coadditive selected from the groupconsisting of polyethylene glycols and polyglycol ethers.
 20. Thepigment concentrate according to claim 17, wherein the at least onecoadditive is present in an amount of from about 0.1 to about 30% byweight, based on the total weight of the pigment concentrate.